TW200908820A - Printed wiring board and electronic device - Google Patents

Abstract

Provided is a printed wiring board (100) which can be bent in a prescribed bending direction (B). The printed wiring board (100) is provided with a fiber base material (2), which has a fiber base material containing first fiber (6) arranged in a first direction (A), and a second fiber (8) arranged in a second direction (C) intersecting with the first direction (A); a conductor layer (4) formed on the fiber base material (2); and a conductor layer (4) formed on the fiber base material (2). In the printed wiring board, the first fiber (6) is arranged to have an angle (?1) formed by the first direction and the bending direction within a range of 30-60 degrees.

Description

200908820 九、發明說明 【發明所屬之技術領域】 本發明係關於印刷配線板及具備折曲的印刷配線板之 電子機器。 【先前技術】 印刷配線板係將電氣絕緣性樹脂組成物等作爲基塊（ matrix)之預浸材（prepreg)，藉由施以加熱加壓等所得 。藉由減成法（s u b t r a c t i v e m e t h 〇 d )形成印刷配線板時， 通常使用覆金屬箔層合板。此覆金屬箔層合板係重疊銅等 之金屬箔於預浸材的表面（單面或兩面），藉由加熱加壓 所製造。作爲電氣絕緣性樹脂，雖常使用如酚醛樹脂、環 氧樹脂、聚醯亞胺樹脂、雙馬來醯亞胺一三氮雜苯樹脂（ bismaleimide-triazine resin)等之熱硬化性樹脂，但因應 所需特性，亦可使用如氟樹脂或聚苯醚（polyphenylene ether )樹脂等之熱可塑性樹脂。 如此之印刷配線板係隨著個人電腦或行動電話等之資 訊末端機器的普及，逐漸發展小型化、高密度化。該封裝 形態係由引腳***型（pin-through-hole )轉型成表面封 裝型，進而逐漸轉型成使用塑膠基板之BGA (球柵陣列 )所代表之面矩陣（area array)式。直接封裝如BGA之 裸晶之印刷配線板中，晶片與印刷配線板之連接，一般係 藉由熱超音波壓著之引線接合（wire bonding)而進行。 因此，封裝裸晶之印刷配線板係暴露於1 5 0 °C以上之高溫 200908820 ，所以要求具備耐熱性。 另外，對於印刷配線板，有時亦要求暫時取 晶片，即所謂的修復性。如此之印刷配線板，於 時，施以與晶片封裝時相同程度的熱，之後，爲 封裝，再次施以熱處理。因此，對於要求修復性 線板，要求亦具備有於高溫之循環耐熱衝擊性。 相關情況下，爲提升耐熱衝擊性、耐回流（ 性、耐斷裂性，揭示使纖維基材含浸以聚醯胺醯 要成份之樹脂組成物之預浸材（例如參考專利文 使纖維基材含浸由聚矽氧烷改性聚醯亞胺樹脂及 樹脂所成樹脂組成物之耐熱性基材（例如參考專 )等。 另一方面，隨著電子機器的小型化、高性能 於有限的空間，收納施以零件封裝之印刷配線板 刷配線板之薄型化。爲因應相關要求，開發印刷 之薄基材，亦供給厚度爲1 0 // m程度之玻璃布 合此等薄纖維基材與具有可動性樹脂，可提升印 之折曲特性。 另外’爲提升印刷配線板之收納性，採取配 數之印刷配線板' 錯由線材加工（w i r e h a r n e s s 配線板相互連接之方法。另外，可使用多層化以 爲基底之撓性基板與傳統之硬質基板之剛撓基板 對於電子機器之小型化、高性能化，可任意折曲 線板扮演重要的角色。 下封裝之 取下晶片 再度晶片 之印刷配 reflow ) 亞胺爲必 獻1 )、 熱硬化性 利文獻2 化，必須 ，要求印 配線板用 。揭示組 刷配線板 置多層複 )或撓性 聚醯亞胺 。如此地 之印刷配 -5- 200908820 專利文獻1 :特開20 03 — 5 548 6號公報 專利文獻2 :特開平8 — 1 93 1 3 9號公報 【發明內容】 發明之揭示 發明所欲解決之課題 然而，電子機器逐漸發展更加小型化、高性能化’爲 使框體內更高密度地收納印刷配線板，所以尋求可任意折 曲且具有優異尺寸安定性之印刷配線板。 本發明係有鑑於上述情況所實施者，以提供可任意折 曲，同時具有充分的尺寸安定性，充分提升耐折性之印刷 配線板爲目的。另外，本發明係以提供具備折曲的該印刷 配線板之電子機器爲目的。 課題之解決手段 爲達成上述目的，本發明提供於預定折曲方向折曲的 印刷配線板，具備含有配置於第1方向的第1纖維之纖維 基材、與形成於纖維基材上的導體層，第1纖維爲配置成 使第1方向與折曲方向所成角度爲3 0〜6 0度之印刷配線 板。 因爲如此之印刷配線板係具有纖維基材，所以可任意 曲折，同時具有充分的尺寸安定性。另外，充分提升耐折 性者。本發明者等係如下推測得到相關效果之理由。 圖3係傳統折曲的印刷配線板之上視圖。如圖3所示 -6- 200908820 之傳統折曲的印刷配線板係折曲於預定折曲方向時，纖維 之配置方向與折曲方向所成角度通常爲0度及/或90度。 例如圖3中，纖維76的配置方向與折曲方向B所成角度 0!爲90度，纖維78的配置方向與折曲方向B所成角度 爲〇度。該所成角度爲0度時，亦即折曲方向與纖維的配 置方向成平行時，折曲印刷配線板時，折曲而突出的面所 配置的纖維（圖3爲纖維78)，受到大的拉伸張力，該 纖維有容易斷裂的趨勢。另外，該所成角度爲90度之配 置方向之纖維（圖3爲纖維76 )時，彎曲強度不足，折 曲時印刷配線板有斷裂的趨勢。 但是，因爲本發明之印刷配線板係折曲方向與纖維的 配置方向所成角度爲30〜60度，所以不容易使斷裂，而 且可減輕折曲時，施加於配置於第1方向的第1纖維之拉 伸應力。因此，認爲耐折性非常優異。另外，本發明中所 謂「折曲方向」係指例如搭載折曲狀態之印刷配線板於電子 機器時之折曲方向，相對於印刷配線板之折曲線爲垂直方 向。另外，第1方向與折曲方向之「所成角度」係第1方向 與折曲方向於平行面內所測定之角度中銳角的角度。 另外，本發明中，纖維基材係以更含有配置於與該第 1方向交叉的第2方向之第2纖維爲宜。因爲如此之印刷 配線板係纖維基材更含有配置於與第1方向相異方向的第 2方向之第2纖維，所以分散折曲時發生之拉伸應力於第 1纖維及第2纖維。因此耐折性更非常優異。另外，具備 具有分別配置於2個互異方向之第1纖維及第2纖維之纖 200908820 維基材之印刷配線板，對於扭轉之耐性亦優異。 另外，本發明中，以第2纖維爲配置成使上述第2方 向與上述折曲方向所成角度爲30〜60度爲宜。因爲如此 之配線板係第1方向與折曲方向所成角度，以及第2方向 與折曲方向所成角度皆爲3 0〜60度，所以折曲印刷配線 板時，拉伸應力更均勻地分散於第1纖維及第2纖維。因 此可更加提升耐折性。另外，第2方向與折曲方向之「所 成角度」係第2方向與折曲方向於平行面內所測定之角度 中銳角的角度。 另外，本發明之印刷配線板，纖維爲玻璃布，該纖維 基材的厚度爲50#m以下爲宜。纖維若爲玻璃布時，可 減小溫度、吸濕等所伴隨之尺寸變化。另外，厚度若爲 5 0 /z m以下時，可更加提升耐折性。 本發明中係以纖維基材中含浸有熱硬化性樹脂爲宜。 藉此可更提升耐折性。 本發明中，以上述熱硬化性樹脂含有具有縮水甘油基 的樹脂爲宜。藉此可提升印刷配線板之耐熱性及耐熱衝擊 性。 另外’本發明中，以上述熱硬化性樹脂含有具有醯胺 基的樹脂爲宜。藉此可提升印刷配線板之可撓性、耐熱性 、耐發塵性、耐熱衝擊性。 另外’本發明中，以上述熱硬化性樹脂含有具有矽氧 烷鍵的聚醯胺醯亞胺樹脂爲宜。藉此可提升印刷配線板之 可撓性、耐熱性、耐發塵性、耐熱衝擊性。 -8- 200908820 另外，本發明中，以上述熱硬化性樹脂含有丙烯酸樹 脂爲宜。藉此可提升可撓性、耐熱性、耐發塵性及耐熱衝 擊性。 本發明係提供具備於預定的折曲方向經折曲之上述印 刷配線板之電子機器。因爲如此電子機器係具備具有上述 特徵之印刷配線板者，所以可充分防止斷線、斷裂等之不 適狀況。 發明之功效 依據本發明，可得到可任意折曲，同時具有充分的尺 寸安定性，充分提升耐折性之印刷配線板。另外，可得到 具備具有經折曲之上述特徵之印刷配線板之電子機器。 用以實施發明之最佳形態 以下係依情況參考圖式，說明關於本發明之適合貫施 形態。另外，圖式說明中，使用相同符號於相同或相等要 素’省略重複說明。 圖1係表示本發明之印刷配線板之適合實施形態之上 視圖。印刷配線板1 〇〇係具備一對非折曲部20包夾折曲 部4 0及折曲部4 0。 折曲部40係具有由第1纖維6及與該第1纖維6垂 直交叉之第2纖維8所形成之纖維基材、具有該纖維基材 中含浸有熱硬化性樹脂之纖維基材層2、及設置於纖維基 材層2之一面上的導體4。第1纖維6係配置於第1方向 -9 - 200908820 A，第2纖維8係配置於第2方向C。纖維基材層2係於 圖1中配置多數個第1纖維與第2纖維分別以預定的間隔 成垂直方向（厚度方向）。 非折曲部20係電子機器等通常所使用之硬板（rigid b 〇 a r d )(硬印刷配線板）。設置如包夾折曲部4 0之一對 硬印刷配線板係藉由折曲部40，彼此電氣連接。 作爲纖維基材層2中之纖維基材，可使用通常覆金屬 范層合板或多層印刷配線板所使用之織布或不織布等之纖 維基材。纖維基材之材質，亦即，作爲第1纖維6及第2 纖維8之材質，以玻璃、氧化鋁、石棉、硼、矽鋁玻璃、 石夕玻璃、T i r a η 〇纖維、碳化砂、氮化砂、氧化銷等之無機 纖維或芳香族聚醯胺、聚醚醚酮、聚醚醯亞胺、聚醚颯、 碳、纖維素等之有機纖維及此等之混抄系爲宜，其中以玻 璃布尤佳。作爲本發明中之纖維基材係以玻璃布之織布最 好。另外，作爲纖維’亦可爲如塡料之長邊方向長度較短 之纖維。 作爲纖維基材的厚度，以50^111以下爲宜。藉由使 用具有如此厚度之玻璃布，可更加提升印刷配線板丨0 0之 折曲部4 0之柔軟性。 作爲導體4，可舉例通常的銅、銀等之金屬製品。就 提升折曲性之觀點，以導體4的厚度爲1〜3 〇 # m爲宜。 印刷配線板1 0 0係以折曲線D (使圖1之上方或下方 成凸狀）折曲成折曲方向B，例如配置於電子機器。折曲 線D係指通常折曲時發生之折曲線（折線）。垂直於此 -10- 200908820 折曲線之方向爲折曲方向B。但是，不發生折曲線時’例 如與藉由折曲所發生的稜線成垂直之方向，可作爲折曲方 向B。 如圖1所示，於平行第1方向A、第2方向C及折曲 方向B的面中，第1方向A與折曲方向B形成角度Θ!， 第2方向C與折曲方向B形成角度02。另外，於本發明 中，角度Θ!及角度02皆爲銳角，角度Θ,及角度θ2中 至少一方爲30〜60度。以角度及角度雙方皆爲30 〜60度爲宜，以40〜50度尤佳，以45度更好。角度 及角度β 2愈接近4 5度，可提升耐折性及對扭轉之耐性。 另外，上述角度及角度02係可藉由例如以光學顯微 鏡觀察印刷配線板的一面（上面）而確認。 於平行第1方向及第2方向的面中，第1方向與第2 方向所成角度係以30〜90度爲宜，以60〜90度尤佳’以 90度更好。另外，該所成角度係指於平行第1方向與第2 方向的平面爲90度以下之角度。 圖2係折曲印刷配線板之側面圖。如圖2所示之折曲 配線板1 〇 〇，因爲於稜線附近發生的拉伸張力’分散於纖 維基材2所含之第1纖維及第2纖維，所以耐折性優異。 另外，因爲纖維基材層2所含之纖維基材係具有配置於2 個互異方向之第1纖維及第2纖維’所以比由配置於1個 方向之纖維所成之纖維基材，對扭轉之耐性優異。 本實施形態之印刷配線板1 00係可使用纖維基材中含 浸熱硬化性樹脂之預浸材而形成。 -11 - 200908820 含浸於纖維基材之熱硬化性樹脂係使用於印刷配線板 領域一般所使用之絕緣性樹脂，使樹脂組成物硬化所得。 作爲熱硬化性樹脂’可舉例如環氧樹脂、聚醯亞胺樹脂、 不飽和聚酯樹脂、聚胺基甲酸乙酯樹脂、雙馬來醯亞胺樹 脂、雙馬來醯亞胺-三氮雜苯樹脂、酚醛樹脂等。 作爲熱硬化性樹脂’以具有縮水甘油基的樹脂爲宜， 以含有環氧樹脂尤佳。作爲環氧樹脂，可舉例如雙酚A、 漆用酚醛型樹脂、鄰甲酚漆用酚醛型樹脂等之使多元酚或 I4一丁二醇等之多元醇與環氧氯丙院反應所得之聚縮水 甘油醚、使苯二甲酸、六氫苯二甲酸等之多價酸與環氧氯 丙烷反應所得之聚縮水甘油酯、具有胺、醯胺或雜環式氮 鹼之化合物之N-縮水甘油基衍生物、脂環式環氧樹脂等 〇 藉由使用環氧樹脂作爲熱硬化性樹脂，可以1 8 0 °C以 下之溫度使硬化。另外，藉由使用環氧樹脂，可提升熱的 、機械的、電氣的特性。以使用具有2個以上縮水甘油基 之環氧樹脂及其硬化劑、具有2個以上縮水甘油基之環氧 樹脂及其硬化促進劑或具有2個以上縮水甘油基之環氧樹 脂及其硬化劑及硬化促進劑爲宜。環氧樹脂所含之縮水甘 油基愈多愈好，以3個以上尤佳。另外，藉由縮水甘油基 數量，可改變樹脂組成物中環氧樹脂之配合量。一般，環 氧樹脂所含之縮水甘油基愈多’可減少樹脂組成物中環氧 樹脂的配合量。 使環氧樹脂硬化所使用之硬化劑、硬化促進劑係只要 -12- 200908820 與環氧樹脂反應者，或促進硬化者即可，並無特別的限制 ’例如可使用胺類、咪唑類、多官能酚類、酸酐類等。作 爲胺類’可使用雙氰胺（dicyandiamide)、二胺基二苯基 甲烷、脒基脲等。作爲多官能酚類，可使用對苯二酚、間 苯二酚、雙酚 A及此等之鹵化物、與甲醛等之縮合物之 漆用酚醛型樹脂、甲酚型酚醛樹脂等。作爲酸酐類，可使 用苯二甲酸酐、二苯甲酮四羧酸二酐、甲基5_降冰片烯_ 2,3 -一竣酸（methyl himic acid)等。作爲硬化促進劑， 可使用作爲咪唑類之烷基取代咪唑、苯幷咪唑等。 樹脂組成物中硬化劑及硬化促進劑的配合量，若使用 胺類時，以胺的活性氫當量與環氧樹脂之環氧當量約成爲 等量爲宜。使用咪唑作爲硬化促進劑時，非單純地與活性 氫之當量比，通常相對於100質量份之環氧樹脂爲0.001 〜1 〇質量份。另外，使用多官能酚類或酸酐類時，相對 於1當量份之環氧樹脂，以〇 . 6〜1 .2當量之酚性羥基或 羧基爲宜。此等硬化劑及硬化促進劑的配合量若過少時， 未硬化之環氧樹脂殘留，有Tg (玻璃轉移溫度）變低之 趨勢。另一方面，硬化劑及硬化促進劑的配合量若過多時 ，未反應之硬化劑及硬化促進劑殘留，有絕緣性降低之趨 勢。 本實施形態之纖維基材所含浸之熱硬化性樹脂（絕緣 性樹脂），以可提升可動性或耐熱性爲目的，亦可使含高 分子量之樹脂成份。作爲此高分子量之樹脂成份，可舉例 聚醯胺醯亞胺樹脂或丙烯酸樹脂。 -13- 200908820 作爲聚醢胺酿亞胺樹脂’以樹脂中具有砂氧院鍵的石夕 氧烷改性聚醯胺醯亞胺爲宜。尤其以使具有2個以上芳香 族環之二胺及矽氧烷二胺之混合物與偏苯三酸酐反應所得 之含有一醯亞胺二羧酸之混合物’與芳香族二異氰酸酯反 應所得之矽氧烷改性聚醯胺醯亞胺爲宜。 分子中具有矽氧烷結構之矽氧烷改性聚醯胺醯亞胺係 具有2個以上芳香族環之芳香族二胺a與矽氧烷二胺b之 混合莫耳比爲（a/b )係以 99.9/0. 1〜〇/1 〇〇爲宜，以a/b = 95/5〜30/70尤佳，以a/b= 90/10〜40/60更好。矽氧烷 二胺b之混合比率過多時，有樹脂之Tg降低之趨勢。另 外’該混合比率過少時，製作附樹脂之金屬箔時，有樹脂 中殘存清漆溶劑量變多之趨勢。 作爲芳香族二胺，可舉例如2,2 -雙[4 一（4 -胺基苯 氧基）苯基]丙烷（BAPP)、雙[4 — (3 —胺基苯氧基）苯基]颯 、雙[4— (4 一胺基苯氧基）苯基]颯、2,2—雙[4一（4一胺基 苯氧基）苯基]六氟丙烷、雙[4 一（4 一胺基苯氧基）苯基]甲 烷、4,4’ 一雙（4 一胺基苯氧基）聯苯、雙[4 一（4一胺基苯氧 基）苯基]醚、雙[4 一（4 一胺基苯氧基）苯基]酮、1，3 —雙（4 一胺基苯氧基）苯、1，4 一雙（4 一胺基苯氧基）苯、2,2’ 一二 甲基聯苯—4,4’一二胺、2,2’_雙（三氟甲基）聯苯—4,4，— 二胺、2,6,2’，6’ 一四甲基一 4,4’一 二胺、5,5’一二甲基一 2,2’_磺醯一聯苯一4,4’—二胺、3,3’一二羥基聯苯一4,4’ 一二胺、（4,4’ 一二胺基）二苯基醚、（4,4’_二胺基）二苯颯 、（4，4’ 一二胺基）二苯甲酮、（3,3’一二胺基）二苯甲酮、 -14- 200908820 (4,4, 一二胺基）二苯基甲烷、（4,4’ 一二胺基）二苯基醚 (3,3’一二胺基）二苯基醚等。 作爲矽氧烷二胺，可使用例如以下述一般式（1 ) (4 )所示之化合物。 [化1] h2nch2ch2ch2.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring board and an electronic device including a bent printed wiring board. [Prior Art] A printed wiring board is obtained by applying heat, pressure, or the like to a prepreg which is a matrix of an electrically insulating resin composition or the like. When a printed wiring board is formed by a subtractive method (s u b t r a c t i v e m e t h 〇 d ), a metal foil-clad laminate is usually used. This metal foil-clad laminate is formed by laminating a metal foil such as copper on the surface (single or both sides) of the prepreg by heat and pressure. As the electrically insulating resin, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, or a bismaleimide-triazine resin is often used, but As the desired characteristics, a thermoplastic resin such as a fluororesin or a polyphenylene ether resin can also be used. Such a printed wiring board has been gradually reduced in size and density with the spread of information terminal devices such as personal computers and mobile phones. The package form is transformed from a pin-through-hole to a surface mount type, and is gradually transformed into an area array represented by a BGA (Ball Grid Array) using a plastic substrate. In a printed wiring board in which a bare crystal such as a BGA is directly packaged, the connection between the wafer and the printed wiring board is generally performed by wire bonding by thermal ultrasonic pressing. Therefore, the printed wiring board in which the bare crystal is packaged is exposed to the high temperature of 200908820 above 150 °C, so heat resistance is required. Further, in the case of a printed wiring board, it is sometimes required to take a wafer temporarily, that is, so-called repairability. In such a printed wiring board, heat is applied to the same level as in the case of wafer packaging, and then heat treatment is applied again for packaging. Therefore, in order to require a repairable wire board, it is required to have a thermal shock resistance at a high temperature. In the related case, in order to improve thermal shock resistance, reflow resistance (resistance, and fracture resistance, a prepreg in which a fiber substrate is impregnated with a resin composition of a polyamide amine component is disclosed (for example, referring to a patent for impregnating a fiber substrate) A heat-resistant substrate (for example, a reference) in which a resin composition of a polyimide resin is modified by a polysiloxane, and the like, and the electronic device is reduced in size and high in a limited space. The thickness of the printed wiring board brushing board that accommodates the parts package is reduced. In order to meet the requirements, a thin substrate is developed, and a thin fiber substrate having a thickness of about 10 // m is supplied to the thin fiber substrate and a movable resin. In addition, in order to improve the storability of printed wiring boards, a printed wiring board with a matching number is used. The wire is processed by wires (wireharness wiring boards are connected to each other. In addition, multilayering can be used as the base. The rigid substrate of the flexible substrate and the conventional hard substrate plays an important role in the miniaturization and high performance of the electronic device. The package is removed from the wafer and the wafer is reprinted with reflow. The imine is a must. 1). The thermosetting property is 2, and it must be used for printing and distribution boards. It is necessary to disclose the set of brush wiring boards and multilayer flexible or flexible poly Imine. In the case of the above-mentioned invention, the invention is intended to be solved by the invention disclosed in Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. However, the electronic device has been developed to be more compact and higher in performance. In order to accommodate the printed wiring board at a higher density in the casing, a printed wiring board which can be flexibly bent and has excellent dimensional stability is sought. The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a printed wiring board which can be flexibly arbitrarily and which has sufficient dimensional stability and sufficiently improves folding resistance. Further, the present invention has an object of providing an electronic device including the printed wiring board. In order to achieve the above object, the present invention provides a printed wiring board that is bent in a predetermined bending direction, and includes a fiber base material including a first fiber disposed in a first direction and a conductor layer formed on the fiber base material. The first fiber is a printed wiring board that is disposed at an angle of 30 to 60 degrees between the first direction and the bending direction. Since such a printed wiring board has a fibrous base material, it can be arbitrarily bent and has sufficient dimensional stability. In addition, fully improve the folding resistance. The inventors of the present invention have reason to estimate the relevant effects as follows. Figure 3 is a top view of a conventionally folded printed wiring board. As shown in Fig. 3, the conventionally folded printed wiring board of -6-200908820 is bent at a predetermined bending direction, and the angle between the arrangement direction of the fibers and the bending direction is usually 0 degrees and/or 90 degrees. For example, in Fig. 3, the angle between the arrangement direction of the fibers 76 and the bending direction B is 90 degrees, and the angle between the arrangement direction of the fibers 78 and the bending direction B is the degree of twist. When the angle of formation is 0 degrees, that is, when the bending direction is parallel to the direction in which the fibers are arranged, when the printed wiring board is bent, the fibers disposed on the surface that is bent and protruded (the fiber 78 in FIG. 3) are large. The tensile tension of the fiber has a tendency to break easily. Further, when the fiber having the angle of arrangement of 90 degrees (the fiber 76 in Fig. 3) is insufficient, the bending strength is insufficient, and the printed wiring board tends to be broken at the time of folding. However, since the angle of the bending direction of the printed wiring board of the present invention and the direction in which the fibers are disposed is 30 to 60 degrees, it is not easy to be broken, and when the bending is reduced, the first direction is placed in the first direction. The tensile stress of the fiber. Therefore, it is considered that the folding endurance is very excellent. In the present invention, the "bending direction" refers to, for example, a bending direction in which a printed wiring board in a bent state is mounted on an electronic device, and a vertical direction with respect to a folding line of the printed wiring board. Further, the "angle formed" of the first direction and the bending direction is an angle of an acute angle between the first direction and the angle of the bending direction measured in the parallel plane. Further, in the present invention, the fiber base material preferably contains the second fiber disposed in the second direction intersecting the first direction. Since the printed wiring board-based fiber base material further includes the second fiber disposed in the second direction in the direction different from the first direction, the tensile stress generated when the bending is dispersed is applied to the first fiber and the second fiber. Therefore, the folding endurance is more excellent. Further, a printed wiring board having a base material having a first fiber and a second fiber disposed in two mutually different directions is excellent in torsion resistance. Further, in the invention, it is preferable that the second fiber is disposed such that the angle between the second direction and the bending direction is 30 to 60 degrees. Since the wiring board has an angle formed by the first direction and the bending direction, and the angle between the second direction and the bending direction is 30 to 60 degrees, the tensile stress is more uniformly bent when the printed wiring board is bent. Dispersed in the first fiber and the second fiber. Therefore, the folding endurance can be further improved. Further, the "angle formed" between the second direction and the bending direction is an angle of an acute angle between the second direction and the angle of the bending direction measured in the parallel plane. Further, in the printed wiring board of the present invention, the fiber is a glass cloth, and the thickness of the fiber base material is preferably 50 #m or less. When the fiber is a glass cloth, the dimensional change accompanying temperature, moisture absorption, and the like can be reduced. Further, when the thickness is 5 0 /z m or less, the folding endurance can be further improved. In the present invention, it is preferred that the fibrous base material is impregnated with a thermosetting resin. This can further improve the folding resistance. In the present invention, it is preferred that the thermosetting resin contains a resin having a glycidyl group. Thereby, the heat resistance and thermal shock resistance of the printed wiring board can be improved. Further, in the present invention, it is preferred that the thermosetting resin contains a resin having a guanamine group. Thereby, the flexibility, heat resistance, dust resistance, and thermal shock resistance of the printed wiring board can be improved. Further, in the present invention, it is preferred that the thermosetting resin contains a polyamidoximine resin having a siloxane bond. Thereby, the flexibility, heat resistance, dust resistance, and thermal shock resistance of the printed wiring board can be improved. Further, in the present invention, it is preferred that the thermosetting resin contains an acrylic resin. This improves flexibility, heat resistance, dust resistance and heat shock resistance. The present invention provides an electronic apparatus having the above-described printed wiring board which is bent in a predetermined bending direction. Since the electronic device is provided with the printed wiring board having the above characteristics, it is possible to sufficiently prevent an unsuitable situation such as disconnection or breakage. EFFECT OF THE INVENTION According to the present invention, it is possible to obtain a printed wiring board which can be flexibly arbitrarily and which has sufficient dimensional stability and sufficiently improves folding resistance. Further, an electronic device having a printed wiring board having the above-described characteristics of being bent can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION The following is a description of a suitable embodiment of the present invention with reference to the drawings. In the drawings, the same reference numerals are used for the same or equivalent elements, and the repeated description is omitted. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a top plan view showing a suitable embodiment of a printed wiring board of the present invention. The printed wiring board 1 includes a pair of non-folded portions 20 that sandwich the bent portion 40 and the bent portion 40. The bent portion 40 has a fiber base material formed of the first fiber 6 and the second fiber 8 perpendicularly intersecting the first fiber 6, and the fiber base material layer 2 having the fiber base material impregnated with the thermosetting resin And a conductor 4 disposed on one surface of the fibrous base material layer 2. The first fiber 6 is disposed in the first direction -9 - 200908820 A, and the second fiber 8 is disposed in the second direction C. In the fiber base material layer 2, a plurality of the first fibers and the second fibers are arranged in a vertical direction (thickness direction) at predetermined intervals in Fig. 1 . The non-bending portion 20 is a rigid board (hard printed wiring board) which is generally used in an electronic device or the like. The pair of hard printed wiring boards, such as one of the package bending portions 40, are electrically connected to each other by the bent portion 40. As the fiber base material in the fiber base material layer 2, a fiber base material such as a woven fabric or a nonwoven fabric which is usually used for a metal-clad laminate or a multilayer printed wiring board can be used. The material of the fiber base material, that is, the material of the first fiber 6 and the second fiber 8, and glass, alumina, asbestos, boron, yttrium aluminum glass, Shishi glass, T ira η 〇 fiber, carbonized sand, nitrogen An inorganic fiber such as a chemical sand or an oxidized pin, or an organic fiber such as an aromatic polyamine, a polyether ether ketone, a polyether phthalimide, a polyether oxime, a carbon, or a cellulose, and the like, and a mixed system thereof, wherein Glass cloth is especially good. The fiber substrate in the present invention is preferably a woven fabric of glass cloth. Further, the fiber ' may be a fiber having a short length in the longitudinal direction of the crucible. The thickness of the fibrous base material is preferably 50^111 or less. By using the glass cloth having such a thickness, the flexibility of the bent portion 40 of the printed wiring board 丨0 0 can be further improved. As the conductor 4, a general metal product such as copper or silver can be exemplified. From the viewpoint of improving the flexibility, it is preferable that the thickness of the conductor 4 is 1 to 3 〇 #m. The printed wiring board 100 is bent in a bending direction B (in a convex shape above or below the drawing 1), and is disposed, for example, in an electronic device. The bending line D is a folding curve (polyline) that occurs when bending is usually performed. Vertically here -10- 200908820 The direction of the bend curve is the bend direction B. However, when the folding curve does not occur, for example, a direction perpendicular to the ridge line generated by the bending can be used as the bending direction B. As shown in FIG. 1, in the plane parallel to the first direction A, the second direction C, and the bending direction B, the first direction A and the bending direction B form an angle Θ!, and the second direction C and the bending direction B form. Angle 02. Further, in the present invention, the angle Θ! and the angle 02 are both acute angles, angle Θ, and at least one of the angles θ2 is 30 to 60 degrees. Both angles and angles are preferably 30 to 60 degrees, preferably 40 to 50 degrees, and more preferably 45 degrees. The closer the angle and angle β 2 is to 45 degrees, the better the folding resistance and the resistance to torsion. Further, the above angle and angle 02 can be confirmed by, for example, observing one side (upper surface) of the printed wiring board with an optical microscope. In the plane parallel to the first direction and the second direction, the angle formed by the first direction and the second direction is preferably 30 to 90 degrees, more preferably 60 to 90 degrees, and even more preferably 90 degrees. In addition, the angle formed by the angle is an angle of 90 degrees or less in a plane parallel to the first direction and the second direction. Figure 2 is a side view of a bent printed wiring board. The bent wiring board 1 〇 所示 shown in Fig. 2 is excellent in folding resistance because the tensile tension generated in the vicinity of the ridge line is dispersed in the first fiber and the second fiber contained in the fiber base material 2. In addition, since the fiber base material contained in the fiber base material layer 2 has the first fiber and the second fiber disposed in two mutually different directions, it is a fiber base material formed by fibers disposed in one direction, and Excellent resistance to twisting. The printed wiring board 100 of the present embodiment can be formed by using a prepreg containing a thermosetting resin in a fiber base material. -11 - 200908820 A thermosetting resin impregnated on a fiber base material is used for curing a resin composition by using an insulating resin generally used in the field of printed wiring boards. Examples of the thermosetting resin include epoxy resin, polyimide resin, unsaturated polyester resin, polyurethane resin, bismaleimide resin, and bismaleimide-trinitrogen. A benzene resin, a phenol resin, or the like. The thermosetting resin 'is preferably a resin having a glycidyl group, and it is particularly preferable to contain an epoxy resin. Examples of the epoxy resin include a phenol, a phenolic resin for lacquer, and a phenolic resin for o-cresol lacquer, which are obtained by reacting a polyhydric alcohol such as a polyhydric phenol or I4-butanediol with an epoxy chlorin. N-shrinkage of a polyglycidyl ester obtained by reacting a polyvalent acid such as polyglycidyl ether, phthalic acid or hexahydrophthalic acid with epichlorohydrin, or a compound having an amine, a guanamine or a heterocyclic nitrogen base A glyceryl derivative or an alicyclic epoxy resin can be cured at a temperature of 180 ° C or lower by using an epoxy resin as a thermosetting resin. In addition, thermal, mechanical, and electrical properties can be enhanced by using epoxy resins. An epoxy resin having two or more glycidyl groups and a hardener thereof, an epoxy resin having two or more glycidyl groups, a hardening accelerator, or an epoxy resin having two or more glycidyl groups and a hardener thereof And a hardening accelerator is preferred. The more the condensed glycerin base contained in the epoxy resin, the better, preferably three or more. Further, the amount of the epoxy resin in the resin composition can be changed by the amount of the glycidyl group. In general, the more the glycidyl group contained in the epoxy resin is, the less the amount of the epoxy resin in the resin composition can be reduced. The hardener and the hardening accelerator used for curing the epoxy resin are only required to react with the epoxy resin in the period of -12-200908820, or to promote hardening, and there is no particular limitation. For example, amines, imidazoles, and the like can be used. Functional phenols, acid anhydrides, and the like. As the amine, 'dicyandiamide, diaminodiphenylmethane, guanylurea or the like can be used. As the polyfunctional phenol, a phenolic resin for varnish, a cresol novolac resin, or the like which is a condensate of hydroquinone, resorcin, bisphenol A, or the like, and a condensate with formaldehyde or the like can be used. As the acid anhydride, phthalic anhydride, benzophenonetetracarboxylic dianhydride, methyl-5-norbornene, methyl himic acid or the like can be used. As the hardening accelerator, an alkyl-substituted imidazole or benzoimidazole which is an imidazole can be used. When the amount of the curing agent and the curing accelerator in the resin composition is used, when an amine is used, the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are preferably equal to each other. When imidazole is used as the hardening accelerator, the equivalent ratio of the non-pure to the active hydrogen is usually 0.001 to 1 part by mass based on 100 parts by mass of the epoxy resin. Further, when a polyfunctional phenol or an acid anhydride is used, it is preferred to use a phenolic hydroxyl group or a carboxyl group of from 6 to 1.2 equivalents per equivalent of the epoxy resin. When the amount of the curing agent and the curing accelerator is too small, the unhardened epoxy resin remains and the Tg (glass transition temperature) tends to be low. On the other hand, when the amount of the curing agent and the curing accelerator is too large, the unreacted curing agent and the curing accelerator remain, and the insulating property tends to be lowered. The thermosetting resin (insulating resin) impregnated in the fiber base material of the present embodiment may have a high molecular weight resin component for the purpose of improving the mobility or heat resistance. As the high molecular weight resin component, a polyamidoximine resin or an acrylic resin can be exemplified. -13- 200908820 As the polyamido-bromide resin, it is preferred to use a sulfoximine-modified polyamidoximine having a sand-oxygen bond in the resin. In particular, a decane modification obtained by reacting a mixture of a quinone imine dicarboxylic acid obtained by reacting a mixture of a diamine and a decane diamine having two or more aromatic rings with trimellitic anhydride with an aromatic diisocyanate Polyamidoximine is preferred. a mixed oxime oxime imine having a decane structure in a molecule, wherein the molar ratio of the aromatic diamine a having two or more aromatic rings to the fluorinated diamine b is (a/b) ) is preferably 99.9/0. 1~〇/1 ,, especially a/b = 95/5~30/70, better with a/b= 90/10~40/60. When the mixing ratio of the oxime diamine b is too large, the Tg of the resin tends to decrease. Further, when the mixing ratio is too small, when a metal foil with a resin is produced, the amount of the varnish solvent remaining in the resin tends to increase. The aromatic diamine may, for example, be 2,2-bis[4-mono(4-aminophenoxy)phenyl]propane (BAPP) or bis[4-(3-aminophenoxy)phenyl] Bismuth, bis[4-(4-aminophenoxy)phenyl]indole, 2,2-bis[4-mono(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(4) Monoaminophenoxy)phenyl]methane, 4,4'-bis(4-monoaminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[ 4-(4-monophenoxy)phenyl]one, 1,3-bis(4-monoaminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2, 2'-Dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)biphenyl-4,4,-diamine, 2,6,2',6' Tetramethyl- 4,4'-diamine, 5,5'-dimethyl- 2,2'-sulfonate-biphenyl-4,4'-diamine, 3,3'-dihydroxybiphenyl 4,4'-diamine, (4,4'-diamino)diphenyl ether, (4,4'-diamino)diphenyl hydrazine, (4,4'-diamino)diphenyl Ketone, (3,3'-diamino)benzophenone, -14- 200908820 (4,4, monoamino)di Phenylmethane, (4,4'-diamino)diphenyl ether (3,3'-diamino)diphenyl ether or the like. As the nonoxyldiamine, for example, a compound represented by the following general formula (1) (4) can be used. [Chemical 1] h2nch2ch2ch2.

Si-CH2CH2CH2NH2 CH3 ⑴ [式中，η係表示1〜50之整數]。 [化2] h2nch2ch2ch2Si-CH2CH2CH2NH2 CH3 (1) [wherein η represents an integer of 1 to 50]. [2] h2nch2ch2ch2

c6h5 I Si-CH2CH2CH2NH2 c6hs (2) [式中，m係表示1〜50之整數]。 [化3]C6h5 I Si-CH2CH2CH2NH2 c6hs (2) wherein m is an integer from 1 to 50. [Chemical 3]

(3) [式中，k係表示1〜50之整數]。 [化4] h2nch2ch2ch2(3) [where k is an integer of 1 to 50]. [化4] h2nch2ch2ch2

Si 一 0· C6H5 JSi a 0· C6H5 J

ch3 I Si-CH2CH2CH2NH2 ch3 (4) [式中，q及r係分別獨立，表示1〜40之整數，且2$ -15- 200908820 + r < 5 0 ]。 作爲上述一般式（1 )所示之矽氧烷二胺 X— 22— 161AS (胺當量：450) 、X— 22— 16 1 :840) 、X—22— 161B(胺當量：1500)(. 化學工業股份有限公司製，商品名）、：BY 1 6 -量：650) 、BY16— 853B (胺當量：2200)Ch3 I Si-CH2CH2CH2NH2 ch3 (4) [wherein, q and r are independent, each represents an integer from 1 to 40, and 2$ -15- 200908820 + r < 5 0 ]. As the above general formula (1), the oxirane diamine X-22-161AS (amine equivalent: 450), X-22-16: 840), X-22-161B (amine equivalent: 1500) (. Chemical Industry Co., Ltd., trade name), BY 1 6 - quantity: 650), BY16 - 853B (amine equivalent: 2200)

Toray Dow Corning Silicone 股份有限公司製 等。上述一般式（4)所示之砂氧院二胺，可I 22— 9409 (胺當量:700 ) 、X— 22—1660B — :22 00 )(以上爲信越化學工業股份有限公司 )等。 作爲用以得到矽氧烷改性聚醯胺醯亞胺樹 二胺類，可使用以下述一般式（5 )所示之化合 WL5] ，可舉例如 [A (胺當量 以上爲信越 -853 (胺當 (以上爲 '商品名） 畢例如 X — 3 (胺當量 製，商品名 脂之脂肪族 -物。Toray Dow Corning Silicone Co., Ltd., etc. The aerobic diamine represented by the above general formula (4) may be I 22-9409 (amine equivalent: 700), X-22-1660B -: 22 00 (the above is Shin-Etsu Chemical Co., Ltd.) and the like. As the polyoxamine iminoamine diamine to be used for obtaining a decane, a compound WL5] represented by the following general formula (5) can be used, and for example, [A (amine equivalent or more is Shin-Etsu-853 ( The amine (above the 'commodity name') is, for example, X-3 (the amine equivalent system, the aliphatic ester of the trade name ester).

[式中’ X係表示伸甲基、磺醯基、醚基 '羰 R1及R2係分別表示氫原子、烷基、苯基或耳 係表不1〜50之整數]。 作爲一般式（5 )中之R 1及R2，係以氫 爲1〜3之烷基、苯基、取代苯基爲宜。作爲 取代基’可舉例如碳數爲1〜3之烷基、鹵原q 就脂肪族二胺同時成立低彈性率及高Tg 基或單鍵， U戈苯基，p 原子、碳數 取代苯基之 :等。 値之觀點， -16- 200908820 上述一般式（5)中之X係以醚基爲宜。作爲如此脂肪族 二胺，可舉例如JeffamineD — 400 (胺當量400’三井化 學Fine (股）製，商品名）、JeffamineD-2000 (胺當量 1000，三井化學Fine (股）製’商品名）等。 作爲聚醯胺醯亞胺樹脂，以含有70莫耳％以上之一 分子中含有10個以上醯胺基之聚醯胺醯亞胺分子之聚醯 胺醯亞胺樹脂爲宜。該聚醯胺醯亞胺樹脂所含該聚醯胺醯 亞胺分子之含量係可由聚醯胺醯亞胺之GPC (凝膠滲透層 析儀，Gel Permeation Chromatography)所得之色譜，及另 外求得之單位質量中醯胺基之莫耳數（A )而求出。例如 將由聚醯胺醯亞胺樹脂（a) g中所含醯胺基之莫耳數（A )，以式（l〇xa/A )所計算的値，作爲一分子中含有10 個醯胺基之聚醯胺醯亞胺分子之分子量（C)。此時，以 GPC所得色譜之數量平均分子量爲上述分子量（C )以上 區域之比率係成爲含有1 〇個以上胺基之聚醯胺醯亞胺分 子之含量。另外，醯胺基之莫耳數（A)之定量方法係可 使用 NMR (核磁共振）、IR (紅外線）、氫氧胺酸（ hydroxamic acid)—鐵呈色反應法、N —溴醯胺法等。 上述GP C (凝膠滲透層析儀）之測定係以下述測定裝 置及測定條件進行。 偵測器：L — 7490 (日立製作所股份有限公司製） 管柱：GL- S 3 00MDT— 5 (日立化成股份有限公司製 ，串聯2支使用） 沖提液：含有〇·6〇Μ之H3P04及0.30M之LiBr之 -17- 200908820 DMF/THF 混合液[DMF/THF= 1/1 (體積比）] 測定溫度：30°C 試料濃度：〇.2mg/l ml 注入量：1 〇 〇 # 1 壓力：4MPa 流量：1 m 1 /分 作爲使用於製造本發明之聚醯胺醯亞胺樹脂之異氰酸 酯係可使用下述一般式（6 )所示之化合物。 _ OCN—D—NCO (6) [式中，D係具有至少1個芳香環之2價有機基、或2價 脂肪族烴基]。 作爲上述一般式（6 )所示之2價基係以至少1種選 自以一C6H4 — CH2 — C6H4 —所表示的基、伸苯甲基（ 1;〇1丫161^)、伸萘基、六伸甲基、2,2,4—二甲基六伸甲基 及異佛爾酮基所成群的基爲宜。 上述一般式（6)所示之二異氰酸酯’可使用脂肪族 二異氰酸酯或芳香族二異氰酸酯。其中以使用芳香族二異 氰酸酯爲宜，以倂用脂肪族二異氰酸酯及芳香族二異氰酸 酯尤佳。 作爲芳香族二異氰酸酯’可舉例如4,4’-二苯基甲烷 二異氰酸酯（MDI) 、2,4 一伸苯甲基二異氰酸酯、2,6 — 伸苯甲基二異氰酸酯、萘一 1，5—二異氰酸酯、2,4-伸苯 甲基二聚物等。此等舉例物中，以使用 MDI爲宜。藉由 -18- 200908820 使用MDI作爲芳香族二異氰酸醋’可更提升所得聚酿胺 醯亞胺樹脂之可撓性。 作爲脂肪族二異氰酸酯，可舉例如六伸甲基二異氰酸 酯、2,2,4 一三甲基六伸甲基二異氰酸酯、異佛爾酮二異 氰酸酯等。 倂用芳香族二異氰酸酯及脂肪族二異氰酸酯時，相對 於芳香族二異氰酸酯，添加5〜10莫耳％程度之脂肪族二 異氰酸酯爲宜。藉由倂用芳香族二異氰酸酯及脂肪族二異 氰酸酯，可更加提升所得聚醯胺醯亞胺樹脂之耐熱性。 作爲丙烯酸樹脂，可使用丙烯酸單體、甲基丙烯酸單 體、丙烯腈、具有縮水甘油基之丙烯酸單體等之單獨或此 等複數共聚合之共聚物。分子量雖非特別的限定者，但以 使用以GPC (凝膠滲透層析儀）所求出之標準聚苯乙烯換 算之重量平均分子量爲30萬〜100萬者爲宜，以使用40 萬〜80萬者尤佳。另外，此時之GPC測定係將3支GMH XL ( Toray股份有限公司製）串聯而進行，可使用THF 作爲沖提劑進行。另外，以加入環氧樹脂、硬化劑、硬化 促進劑於此等丙烯酸樹脂使用爲宜。 另外’以提升難燃性爲目的，亦可使用添加型之難燃 劑。作爲添加型之難燃劑，可適用含磷之塡料。作爲含磷 之塡料’可舉例如OP9 3 0 ( Clariant公司製，商品名，含 磷量：23.5質量％ ) 、HCA— HQ (三光股份有限公司製， 商品名，含磷量：9.6質量％ )、聚磷酸三聚氰胺PMP -100(含磷量：13.8質量％) 、PMP - 200 (含磷量：9_3 -19- 200908820 質量％) 、？1^?一3〇〇(含磷量：9_8質量％)( 產化學股份有限公司製’商品名等）。 製造本實施形態之印刷配線板之方法之一例 下。 首先，使纖維基材含浸熱硬化性樹脂組成物 於80 °C〜180 °C之範圍乾燥，製造預浸材。預浸 條件等雖非特別限制者，但以於預浸材中使用於 劑揮發80質量％以上爲宜。製造方法或乾燥條 特別限制，乾燥時之溫度爲80 °C〜1 80 °C，時間 清漆之膠化時間而調整。清漆之含浸量係使相對 形物與纖維基材之總重，清漆固形物爲3 0〜8 0 宜。 將如此所得之預浸材，因應需要，層合多片 浸材層合體後，於預浸材層合體之兩面或單面重 藉由加壓層合而可得覆銅層合板。將此藉由通常 術法（Photolithography )電路加工，可得到印 。藉由以通常的方法連接如此可任意折曲之印刷 通常所使用之硬印刷配線板，可得到印刷配線板 以上，雖說明關於本發明之適合實施形態， 並非侷限於上述實施形態者。例如上述實施形態 基材雖以配置方向互異之二種纖維所組成，但纖 可爲僅以配置成同一方向之纖維所組成者。此時 纖維配置的方向與折曲方向所成角度爲30〜60 到本發明之效果。另外，纖維基材除了第1方向 以上爲曰 ，說明如 之清漆， 材之製造 清漆之溶 件等並無 係可兼顧 於清漆固 質量％爲 ，得到預 疊銅范， 的微影技 刷配線板 配線板與 100 ° 但本發明 中，纖維 維基材亦 ，藉由該 度，可得 及第2方 -20- 200908820 向以外，亦可含有配列成其他方向之纖維。此時，纖維基 材中最密集設置之纖維（主纖維）之配置方向與折曲方向 所成角度係以30〜60度爲宜。 【實施方式】 實施例 以下係基於實施例及比較例更具體地說明本發明’但 本發明並非侷限於下述實施例者。 (清漆配合例1 ) 配合22.44kg之聚醯胺醯亞胺樹脂（日立化成工業股 份有限公司製，商品名：KS 990 0B ’樹脂固形物：31.2質 量％ ) 、2.0kg之環氧樹脂之EPPN502H (日本化藥股份有 限公司製，商品名）之甲基乙基酮溶液（樹脂固形物：5 0 質量％) 、3.0kg之HP4032DC大日本INK化學工業股份 有限公司製，商品名）、1.0kg之NC3000 (日本化藥股份 有限公司製，商品名）之甲基乙基酮溶液（樹脂固形物： 50質量％)、及8.0g之1一氰乙基一 2—乙基一 1 一甲基咪 唑，約攪拌1小時直至樹脂成份均勻後，於室溫（25 °C ) 靜置2 4小時以去泡，得到樹脂組成物清漆。 (清漆配合例2 ) 配合22.44kg之聚醯胺醯亞胺樹脂（日立化成工業股 份有限公司製，商品名：KS9900B ’樹脂固形物·· 3丨·2質 -21 - 200908820 量。/。）、2.0kg之環氧樹脂之EPPN5 02H (日本化藥股份有 限公司製，商品名）之甲基乙基酮溶液（樹脂固形物：5 〇 質量°/〇) 、3.0kg之HP4〇32D(大日本INK化學工業股份 有限公司製，商品名）、1.0kg之NC3000 (日本化藥股份 有限公司製，商品名）之甲基乙基酮溶液（樹脂固形物： 5〇質量％)、及8.0g之1一氰乙基一2—乙基一 甲基咪 口坐’再加入 1.0kg之〇P930 (Clariant公司製，商品名） 、及1 .5kg之HP3 60 (昭和電工股份有限公司製，商品名 )’約攪拌3小時直至樹脂成份均勻後，於室溫（2 5 〇c ) 靜置24小時以去泡，得到樹脂組成物清漆。 (清漆配合例3 ) 溶解3.4kg之作爲環氧樹脂之EPICLON153C大日本 INK股份有限公司製，商品名）、1 . 8 1 g之作爲硬化劑之 FG— 2 000 (帝人化成股份有限公司製，商品名）、lO.Og 之作爲硬化促進劑之1 —氰乙基一 2—苯基咪唑於6.0kg之 甲基異丁基酮後，加入2.87kg之丙烯酸樹脂之HTR— 860 —P3(Nagasechemtex股份有限公司製，商品名）之甲基 乙基酮溶液（樹脂含量：1 5質量。/。），約攪拌1小時直至 樹脂成份均勻。之後，於室溫（2 5 °C )靜置2 4小時以去 泡，得到樹脂組成物清漆。 (清漆配合例4 ) 溶解3.0kg之作爲環氧樹脂之BREN — S (日本化藥股 -22- 200908820 份有限公司製，商品名）、1 . 8 1 kg之作爲硬化費 2000 (帝人化成股份有限公司製，商品名）、1 爲硬化促進劑之1 一氰乙基一 2 —乙基一 1—甲 6.0kg之甲基異丁基酮後，加入2.87kg之丙烯 H TR — 8 6 0 一 Ρ3 (Nagasechemtex 股份有限公司製 )之甲基乙基酮溶液（樹脂含量：15質量％ )， 小時直至樹脂成份均勻。之後，於室溫（2 5 t : 小時以去泡，得到樹脂組成物清漆。 (清漆配合例5 ) 連接回流冷卻器之附有旋塞之25mi之具有 接受窃、溫度§十、攪拌器之5公升分離燒瓶，加 (0.60mol)之作爲具有2個以上芳香族環之二思 (2，2 —雙[4— (4 一胺基苯氧基）苯基]丙烷）、 0_40mol )之作爲矽氧烷二胺之X— 22— 9409 ( 氧烷公司製’商品名，胺當量：700 ) 、3 93.6g )之TMA (偏苯三酸酐）、及23 83 g之作爲非 性溶劑之NMP (N —甲基—2—吡咯烷酮），以 3〇分鐘。接著’加入500ml之作爲可與水共沸 烴之甲苯後’提升溫度，使以約1 60 °C回流2小 分定量接受器飽去3 6.0 m 1以上的水，確認未見 餾出後’提升溫度至約1 9 (Γ C，除去甲苯。之後 得溶液於室溫，加入2 7 5.0 g ( 1 . 1 0 m ο 1 )之作爲 異氰酸酯之MDI(4,4，一二苯基甲烷二異氰酸酯 f!(之 FG -〇.〇g之作 基咪唑於 酸樹脂之 ，商品名 約攪拌1 >靜置24 水分定量 入 246.0g ?之 BAPP 280.0g ( 信越聚矽 (2.0 5 mo1 質子性極 8 0 °C攪拌 之芳香族 時。自水 有新的水 ，恢復所 芳香族二 )於該溶 -23- 200908820 液後’使Μ 1 9G°C反應2小時。反應結束後，得到聚酿胺 醯亞胺樹脂之NMP溶液。 配合2.26kg之聚醯胺醯亞胺樹脂之NMp溶液（樹脂 固形物：31.2質量％) 、〇.2kg之作爲環氧樹脂之 EPPN5 02H (日本化藥股份有限公司製，商品名）（樹脂 固形物爲50質量％之甲基乙基酮溶液）、〇_3kg之 HP403 2D (大日本INK化學工業股份有限公司製，商品名 )、〇.5kg之NC3000 (日本化藥股份有限公司製，商品名 )(樹目曰固形物· 50質量％之甲基乙基嗣溶液）、及0.8g 之丨一氰乙基一2—乙基一1—甲基咪唑，再加入〇 lkg之 OP930 (Clariant 公司製，商品名）、及 〇15kg 之 HP360 (昭和電工股份有限公司製，商品名），約攪拌3小時直 至樹脂成份均勻。之後，於室溫（25 °C )靜置24小時以 去泡，得到樹脂組成物清漆。 (清漆配合例6) 連接回流冷卻器之附有旋塞之25ml之具有水分定量 接受器、溫度計、攪拌器之1公升分離燒瓶，加入3 4 8.5 g (0.85mol)之作爲具有2個以上芳香族環之二胺之BAPP (2,2 —雙[4 一（4 一胺基苯氧基）苯基]丙烷）、330_0g( 0.15mol)之作爲矽氧烷二胺之X— 22 — 1660B— 3(信越 聚矽氧烷公司製’商品名’胺當量2200 )、3 93.6§ ( 2.05mol)之TMA (偏苯三酸酐）、及2600g之作爲非質 子性極性溶劑之N M P ( N -甲基一 2 -吡咯烷酮）’以8 0 -24- 200908820 t：攪拌30分鐘。接著，加入500ml之作爲可與水共沸之 芳香族烴之甲苯後，提升溫度，使以約1 6 〇 °C回流2小時 。自水分定量接受器餾去3 6.0m 1以上的水’確認未見有 新的水餾出後，提升溫度至約19(TC，除去甲苯。之後， 恢復所得溶液於室溫，加入27 5.0g ( 1. lOmol )之作爲芳 香族二異氰酸酯之MDI(4,4’—二苯基甲烷二異氰酸酯） 於該溶液後，使以19(TC反應2小時。反應結束後，得到 聚醯胺醯亞胺樹脂之NMP溶液。 配合2.24kg之聚醯胺醯亞胺樹脂之NMP溶液（樹脂 固形物：31.2質量％ ) 、0_2kg之作爲環氧樹脂之 EPPN5 0 2H (日本化藥股份有限公司製，商品名）（樹脂 固形物爲 50質量％之甲基乙基酮溶液）、〇.3kg之 HP40 3 2D (大日本INK化學工業股份有限公司製，商品名 )、〇.5kg之NC3000 (日本化藥股份有限公司製，商品名 )(樹脂固形物爲5 0質量％之甲基乙基酮溶液）、及 〇.8g之1—氰乙基一 2 —乙基一 1 一甲基咪哩，再加入 0.1kg 之 OP930 (Clariant 公司製，商品名）、及 〇 l5kg 之HP3 60 (昭和電工股份有限公司製，商品名），約攪伴 3小時直至樹脂成份均勻。之後，於室溫（25 °C )靜置24 小時以去泡，得到樹脂組成物清漆。 (製作預浸材） 於玻璃布WEX - 1〇27 (旭shuebel股份有限公司製， 商品名’厚度爲〗9 v m )之兩側主面上，以縱型塗佈機塗 -25 - 200908820 佈清漆配合例1製作之樹脂組成物清漆，使乾燥後之總 度爲55//m’藉由1〇〇〜14〇它之乾燥爐，以滞留時間 分鐘’使加熱、乾燥，得到樹脂含量爲7 1質量％之預 材（P 1 )。同樣地使用清漆配合例2〜6製作之各樹脂 成物清漆’得到樹脂含量爲7 1質量％之預浸材（P 2〜 (樹脂薄膜的製作） 於聚對苯二甲酸乙二醇酯（pET )薄膜（帝人股份 限公司’商品名：Purex31 )上面’將清漆配合例1所 作的樹脂組成物清漆，以壓鑄模塗佈機塗佈至乾燥後的 度5 0 // m ’經1 〇 0〜1 4 〇 〇c的乾燥爐使其5分鐘滯留時 下進行加熱、乾燥而得到樹脂薄膜F1。同樣地，使用 漆配合例2〜6所製作的各樹脂組成物清漆得到樹脂薄 (F2 〜F6)。 (實施例1 ) 以厚度爲1 2 // m之一對電解銅箔（臼本電解股份 限公司製，商品名：HL A — 12)包夾預浸材P1，於預 材P1之兩側主面（與厚度方向成垂直面）上分別層合 電解銅箔’以升溫速度爲5。(： /分、成形溫度爲2 3 0 t、 形壓力爲4MPa、成型時間爲7〇分鐘，真空度爲40hPa 條件’進行加壓’製作兩面覆銅箔層合板。 於此兩面覆銅箔層合板之一側主面（與厚度方向成 厚 10 浸 組 P6 有 製 厚 間 清 膜 有 浸 該 成 之 垂 -26- 200908820 直面）上，藉由鈾刻，形成線寬爲5 0 " m之傳導圖案電 路。此時，於與該主面平行的面，形成傳導圖案電路，以 使雙方之配置玻璃纖維之方向（長邊方向）與傳導圖案電 路之長邊方向所成角度係分別成爲4 5度。於與此製作傳 導圖案電路的面相反側的面，施以全面鈾刻處理，除去銅 箔，製作於一側主面上具有傳導圖案電路之基板材料。 於基板材料之形成傳導圖案的面上，依序層合樹脂薄 膜F1及電解銅箔（日本電解股份有限公司製，商品名： HLA- 12 )，以升溫速度爲5°C /分、成形溫度爲23 0。(：、 成形壓力爲4MPa、成型時間爲70分鐘，真空度爲40hPa 之條件，進行加壓。進行全面蝕刻以除去加壓所得層合板 之表面銅箔，得到以樹脂被覆傳導圖案電路之評估基板。 (實施例2〜6 ) 除了分別使用預浸材P2〜P6以取代預浸材P 1，樹脂 薄膜F2〜6以取代樹脂薄膜F1以外，與實施例1同樣地 得到評估基板。 (實施例7 ) 以厚度爲12/zm之一對電解銅箔（日本電解股份有 限公司製’商品名：HLA - 12)包夾預浸材P1，於預浸 材P1之兩側主面上分別層合該電解銅箔，以升溫速度爲 5°C/分、成形溫度爲230°C、成形壓力爲4MPa、成型時間 爲70分鐘’真空度爲40hPa之條件，進行加壓，製作兩 -27- 200908820 面覆銅箱層合板。 於此兩面覆銅箔層合板之一側主面上，藉由蝕刻，形 成線寬爲5 0 /z m之傳導圖案電路。此時，於與該主面平 行的面，形成傳導圖案電路，以使一側之配置玻璃纖維之 方向（第1方向）與傳導圖案電路之長邊方向（傳導方向 )所成角度成爲3 0度（另一側之配置玻璃纖維之方向與 傳導圖案電路之長邊方向所成角度爲60度）。於與此製 作傳導圖案電路的面相反側的面，施以全面蝕刻處理，除 去銅箔’製作於一側主面上具有傳導圖案電路之基板材料 。使用基板材料，與實施例1同樣地製作評估基板。 (實施例8〜10) 除了分別使用預浸材P 2〜P 4以取代預浸材P 1，樹脂 薄膜F2〜4以取代樹脂薄膜f 1以外，與實施例7同樣地 得到評估基板。 (比較例1〜4 ) P余7 &兩面覆箔層合板之一側主板上，於與該主面平 行的面’形成傳導圖案電路，以使一側之配置玻璃纖維 (圖3之a方向）與傳導圖案電路之長邊方向 (傳導方向）所成角度（圖3之θι)成爲90度以外，與 貫施例1〜4同樣地製作評估基板。 (評估折曲性） -28- 200908820 使用MIT試驗機（東洋精機製作所製，商品名： 2 1 2 1 0 1 1 — 00 )，評估實施例1〜1 0及比較例1〜4之評估 基板之折曲性。此評估試驗中折曲方向（圖1 ,3之B方向 )與一側玻璃纖維（圖1之纖維6，圖3之纖維76)之配 置方向所成角度（0!)(圖1或圖3之01)、及該折曲 方向與另一側玻璃纖維（圖1之纖維8，圖3之纖維7 8 ) 之配置方向所成角度（02)(圖1之θ2，圖3未圖示） 係如表1及表2所示。另外，上述折曲方向係與傳導圖案 電路之長邊方向爲相同方向。相對於彎曲半徑爲0.38mm 或1.00mm，以加重500g、折曲角度爲135度、速度爲 1 75 cpm之條件，分別測定至傳導圖案電路斷線時之折曲 次數及至評估基板斷裂之次數。另外，有無發生斷裂係以 目測判定。結果如表1、2所示。 (評估對扭轉之耐性） 評估實施例1〜1 0及比較例1〜4之評估基板對扭轉 之耐性。此評估試驗中，固定評估基板一側之非折曲部的 端部，以使傳導圖案電路之長邊方向與扭轉之軸方向成平 行，另一側非折曲部之端部施以5 0 0 g之加重狀態，以扭 轉角度+135度〜一 135度，評估至認爲纖維基材斷裂之 次數。另外，有無發生斷裂係以目測判定。結果如表1 ' 2所示。 -29- 200908820 【IS 實施例10 Z § »·〇 Ό >30000 602 >50000 >20000 實施例9 CU § 沄 >30000 487 >50000 >20000 實施例8 (N Cu. S Os >30000 473 >50000 >20000 實施例7 S： 1 >30000 i ί—Η >50000 >20000 實施例6 Ό Oh 00 ] >30000 ί 689 >50000 1 i >20000 實施例5 ίη Οι CN 〇〇 >30000 640 >50000 >20000 實施例4 2 00 1 >30000 , 652 >50000 >20000 實施例3 ΓΛ Ο. CN >30000 570 >50000 >20000 實施例2 (Ν >30000 545 >50000 >20000 實施例1 € 〇〇 >30000 OO in >50000 i >20000 預浸材 角度Θ!(度） 角度θ2 (度） MIT試驗1 (次） （注1) MIT試驗2 (次） （注2) MIT試驗3 (次） （注3) MIT試驗4 (次） （注4) 對扭轉之耐性 （次） 。鉍衫租feiN皲蝱堪«a^>&-lmasl9I:IH^siruttl) 。鐮^租岛^驼鹱蝱槭醒»域_。日日00.1:靼并租||(£玥) 。錳衫租忘忉親蝱惡稍匣担紘ffl。日日oornd: ®并租ifu+H) 。鐮衫租铝忉#0鑛蝱械@1»敏^。日日〇〇「〇:_并«&(1坩) -30- 200908820 [表2] 比較例1 比較例2 比較例3 比較例4 預浸材 Ρ1 Ρ2 Ρ3 Ρ4 角度1 (度） 90 90 90 90 角度θ2 (度） 0 0 0 0 ΜΙΤ試驗1 (次） (注1) 19 16 25 40 ΜΙΤ試驗2 (次） (注2) 8323 8100 10254 10527 ΜΙΤ試驗3 (次） (注3) 197 188 185 230 ΜΙΤ試驗4 (次） (注4) 15132 13501 18644 17546 對扭轉之耐性 (次） 8812 8725 13217 13362 (注1)彎曲半徑：〇.38mm。至傳導圖案斷線時之折曲次數。 (注2)彎曲半徑：0.38mm。至評估用基板斷裂之折曲次數。 (注3)彎曲半徑：1.00mm。至傳導圖案斷線時之折曲次數。 (注4)彎曲半徑：1.00mm。至評估用基板斷裂之折曲次數。 產業上利用性 依據本發明，可提供可任意折曲，同時具有充分的尺 寸安定性，充分提升耐折性之印刷配線板，以及具備具有 折曲之上述特徵之印刷配線板之電子機器。 【圖式簡單說明】 [圖1 ]表示本發明之印刷配線板之適合實施形態之上 視圖。 [圖2]經曲折之印刷配線板之側面圖。 [圖3 ]傳統的經曲折之印刷配線板之上視圖。 【主要元件符號說明】 -31 - 200908820 2 :纖維基材層 4 :導體 6 :第1纖維 8 :第2纖維 20 :非折曲部 40 =折曲部 100，3 00 :印刷配線板 -32[In the formula, X represents a methyl group, a sulfonyl group, and an ether group. 'Carboxylic acids R1 and R2 each represent a hydrogen atom, an alkyl group, a phenyl group or an integer of 1 to 50 in the ear group. R 1 and R 2 in the general formula (5) are preferably an alkyl group having 1 to 3 hydrogen atoms, a phenyl group or a substituted phenyl group. The substituent 'is, for example, an alkyl group having a carbon number of 1 to 3, and a halogen original q. The aliphatic diamine has a low modulus of elasticity and a high Tg group or a single bond, and a U-phenyl group, a p atom, and a carbon number-substituted benzene. Base: Wait. From the viewpoint of 値, -16- 200908820 The X in the above general formula (5) is preferably an ether group. As such an aliphatic diamine, for example, Jeffamine D-400 (amine equivalent 400' manufactured by Mitsui Chemical Fine Co., Ltd., trade name), Jeffamine D-2000 (amine equivalent 1000, manufactured by Mitsui Chemical Fine Co., Ltd.), and the like may be mentioned. . As the polyamidoximine resin, a polyamidoximine resin containing a polyamidoximine molecule having more than 10 guanamine groups in a molecule of 70 mol% or more is preferred. The content of the polyamidoximine molecule contained in the polyamidoximine resin is a chromatogram obtained by GPC (Gel Permeation Chromatography) of polyamidoximine, and is additionally obtained. The molar number (A) of the guanamine group per unit mass was determined. For example, the mole number (A) of the guanamine group contained in the polyamidoximine resin (a) g, the oxime calculated by the formula (l〇xa/A), as 10 molecules of decylamine in one molecule The molecular weight (C) of the polyamidoquinone molecule. In this case, the ratio of the number average molecular weight of the chromatogram obtained by GPC to the above molecular weight (C) or more is the content of the polyamidoximine molecule containing 1 or more amine groups. In addition, the quantitative method of the molar number (A) of the guanamine group can be NMR (nuclear magnetic resonance), IR (infrared), hydroxamic acid-iron color reaction method, N-bromoguanamine method. Wait. The measurement of the above GP C (gel permeation chromatography) was carried out under the following measurement apparatus and measurement conditions. Detector: L — 7490 (manufactured by Hitachi, Ltd.) Column: GL-S 3 00MDT— 5 (made by Hitachi Chemical Co., Ltd., used in series) Evacuation: H3P04 containing 〇·6〇Μ And 0.30M LiBr -17- 200908820 DMF/THF mixed solution [DMF/THF = 1/1 (volume ratio)] Measurement temperature: 30 ° C Sample concentration: 〇. 2 mg / l ml Injection amount: 1 〇〇# 1 Pressure: 4 MPa Flow rate: 1 m 1 /min As the isocyanate used in the production of the polyamidoximine resin of the present invention, the compound represented by the following general formula (6) can be used. _ OCN-D-NCO (6) [wherein D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group]. The divalent group represented by the above general formula (6) is at least one selected from the group consisting of a C6H4-CH2-C6H4-, a benzyl group (1; 〇1丫161^), an anthranyl group. Preferably, a group of a group of a methyl group, a 2,2,4-dimethylhexamethyl group and an isophorone group is preferred. The diisocyanate shown by the above general formula (6) can be an aliphatic diisocyanate or an aromatic diisocyanate. Among them, an aromatic diisocyanate is preferably used, and an aliphatic diisocyanate and an aromatic diisocyanate are preferably used. The aromatic diisocyanate may, for example, be 4,4'-diphenylmethane diisocyanate (MDI), 2,4 benzylidene diisocyanate, 2,6-phenylene diisocyanate, naphthalene-1,5. —diisocyanate, 2,4-extended benzyl dimer, and the like. In these examples, it is preferred to use MDI. By using MDI as the aromatic diisocyanate at -18-200908820, the flexibility of the obtained polyamine amine amide resin can be further improved. The aliphatic diisocyanate may, for example, be hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate. When an aromatic diisocyanate or an aliphatic diisocyanate is used, an aliphatic diisocyanate of about 5 to 10 mol% is preferably added to the aromatic diisocyanate. By using an aromatic diisocyanate and an aliphatic diisocyanate, the heat resistance of the obtained polyamidoximine resin can be further enhanced. As the acrylic resin, a copolymer of a single or a plurality of copolymers of an acrylic monomer, a methacrylic monomer, an acrylonitrile, an acrylic monomer having a glycidyl group, or the like can be used. The molecular weight is not particularly limited, but it is preferably 300,000 to 100,000 by weight average molecular weight in terms of standard polystyrene obtained by GPC (gel permeation chromatography). The 10,000 is especially good. In addition, GPC measurement at this time was carried out by connecting three GMH XL (manufactured by Toray Co., Ltd.) in series, and THF was used as a flushing agent. Further, it is preferred to use an acrylic resin such as an epoxy resin, a curing agent or a curing accelerator. In addition, an additive type of flame retardant may be used for the purpose of improving flame retardancy. As an additive type flame retardant, a phosphorus containing material can be applied. As a phosphorus-containing material, for example, OP9 3 0 (manufactured by Clariant Co., Ltd., product name, phosphorus content: 23.5% by mass), HCA-HQ (manufactured by Sanko Co., Ltd., trade name, phosphorus content: 9.6% by mass) ), melamine polyphosphate PMP-100 (phosphorus content: 13.8% by mass), PMP-200 (phosphorus content: 9_3 -19- 200908820 mass%), ? 1^?-3〇〇 (phosphorus content: 9_8 mass%) (product name, etc. manufactured by Chemical Industry Co., Ltd.). An example of a method of manufacturing the printed wiring board of the present embodiment is as follows. First, the fiber substrate impregnated thermosetting resin composition is dried at a temperature of from 80 ° C to 180 ° C to prepare a prepreg. The prepreg conditions and the like are not particularly limited, but it is preferred that the prepreg is used in an amount of 80% by mass or more. The manufacturing method or the drying bar is particularly limited, and the temperature during drying is 80 ° C to 1 80 ° C, and the gelation time of the varnish is adjusted. The impregnation amount of the varnish is such that the total weight of the relative shape and the fibrous substrate is 30 to 80%. The prepreg thus obtained is laminated with a plurality of sheets of the impregnated material, and a copper clad laminate can be obtained by pressure lamination on both sides or one side of the prepreg laminate. This can be obtained by processing by a conventional photolithography circuit. A printed wiring board can be obtained by connecting a hard printed wiring board which is generally used for printing by such a conventional method. Although a suitable embodiment of the present invention is described, it is not limited to the above embodiment. For example, in the above embodiment, the base material is composed of two kinds of fibers having different arrangement directions, but the fibers may be composed only of fibers arranged in the same direction. At this time, the angle of the fiber arrangement and the direction of the bending are 30 to 60 to the effect of the present invention. In addition, the fiber base material is 曰 in the first direction or more, and it is explained that the varnish, the varnish of the material, and the like are not compatible with the varnish solid mass %, and the lithographic brush wire of the pre-stacked copper is obtained. The board wiring board is 100 °. However, in the present invention, the fiber-dimensional base material is also obtained by the second side of the second to the -20-200908820, and may also contain fibers arranged in other directions. At this time, the angle between the arrangement direction of the fibers (main fibers) which are most densely arranged in the fiber substrate and the direction of the bending is preferably 30 to 60 degrees. [Embodiment] Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. (varnish compounding example 1) 22.44 kg of polyamidoximine imide resin (manufactured by Hitachi Chemical Co., Ltd., trade name: KS 990 0B 'resin solid: 31.2% by mass), 2.0 kg of epoxy resin EPPN502H Methyl ethyl ketone solution (manufactured by Nippon Kayaku Co., Ltd., trade name) (resin solids: 50% by mass), 3.0 kg of HP4032DC manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name), 1.0 kg A methyl ethyl ketone solution (resin solid: 50% by mass) of NC3000 (manufactured by Nippon Kayaku Co., Ltd.), and 8.0 g of 1-cyanoethyl-2-ethyl-1-methyl group The imidazole was stirred for about 1 hour until the resin composition was uniform, and then allowed to stand at room temperature (25 ° C) for 24 hours to be defoamed to obtain a resin composition varnish. (varnish mixture example 2) A 22.44 kg polyacrylamide imine resin (manufactured by Hitachi Chemical Co., Ltd., trade name: KS9900B 'resin solids · · 3丨 · 2 quality-21 - 200908820 quantity. /.) , 2.0kg epoxy resin EPPN5 02H (manufactured by Nippon Kayaku Co., Ltd., trade name) methyl ethyl ketone solution (resin solids: 5 〇 mass ° / 〇), 3.0 kg HP4 〇 32D (large Methyl ethyl ketone solution (resin solid: 5 〇 mass%) of 8.0 g of NC3000 (manufactured by Nippon Kayaku Co., Ltd., trade name) manufactured by INK Chemical Industry Co., Ltd., Japan, and 8.0 g 1 cyanoethyl 2-ethyl-methyl propyl sulphate 'Additional 1.0 kg of 〇P930 (manufactured by Clariant Co., Ltd., trade name), and 1.5 kg of HP3 60 (Showa Denko Co., Ltd., product Name) 'Agitated for about 3 hours until the resin composition was uniform, and allowed to stand at room temperature (25 〇c) for 24 hours to defoam, thereby obtaining a resin composition varnish. (Varnish varnishing example 3) Dissolving 3.4 kg of EPICLON 153C as an epoxy resin, manufactured by Dainippon Ink Co., Ltd., trade name), 1.8 g of FG-2 000 as a curing agent (manufactured by Teijin Chemical Co., Ltd., Product name), lO.Og as a hardening accelerator 1 - cyanoethyl-2-phenylimidazole in 6.0 kg of methyl isobutyl ketone, adding 2.87 kg of acrylic resin HTR-860-P3 (Nagasechemtex A methyl ethyl ketone solution (resin content: 15 mass%) of a company made by Co., Ltd., was stirred for about 1 hour until the resin composition was uniform. Thereafter, it was allowed to stand at room temperature (25 ° C) for 24 hours to be defoamed to obtain a resin composition varnish. (varnish with the example 4) Dissolve 3.0 kg of BREN-S epoxy resin (made by Nippon Chemical Co., Ltd. - 200908820 Co., Ltd., trade name), and 1.81 kg as hardening fee 2000 (Emperor Chemicals Co., Ltd.) Co., Ltd., the product name), 1 is a hardening accelerator 1 - cyanoethyl-2-ethyl- 1 - methyl 6.0 kg of methyl isobutyl ketone, adding 2.87 kg of propylene H TR - 8 6 0 A solution of methyl ethyl ketone (resin content: 15% by mass) of 3 (manufactured by Nagasechemtex Co., Ltd.) for an hour until the resin component was uniform. Thereafter, the resin composition varnish was obtained at room temperature (2 5 t: hour to obtain a resin composition varnish. (Varnish varnish 5). A liter separation flask was added (0.60 mol) as a bismuth (2,2-bis[4-(4-aminophenoxy)phenyl)propane) having 2 or more aromatic rings, 0-40 mol) Oxidane diamine X-22-9409 (trade name "amine name: amine equivalent: 700", 3 93.6g) of TMA (trimellitic anhydride), and 23 83 g of non-solvent NMP (N-A Base-2-pyrrolidone) in 3 minutes. Then, after adding 500 ml of toluene which can azeotrope the hydrocarbon with water, the temperature was raised, and the water was refluxed at about 1 60 ° C for 2 minutes, and the water was taken up to 3 6.0 m 1 or more, and it was confirmed that no distillate was observed. Raise the temperature to about 1 9 (Γ C, remove toluene. Then obtain a solution at room temperature, add 2 7 5.0 g (1.10 m ο 1 ) of MDI as isocyanate (4,4, diphenylmethane II Isocyanate f! (FG - 〇. 〇g as imidazole in acid resin, the trade name is about 1 stirring; > standing 24 moisture quantitatively into 246.0g? BAPP 280.0g (Xin Yue Ju 矽 (2.0 5 mo1 proton When the aromatics are stirred at a temperature of 80 ° C. There is new water from the water to recover the aromatics. 2) After the solution is dissolved in -23-200908820, the reaction is carried out for 2 hours at a temperature of 1 9 G ° C. After the reaction is completed, the polymerization is completed. NMP solution of amine amine imide resin. NMp solution (resin solids: 31.2% by mass) with 2.26kg of polyamidoximine resin, PN.2kg of EPPN5 02H as epoxy resin (Nippon Chemical Co., Ltd.) Co., Ltd., trade name) (resin solids are 50% by mass of methyl ethyl ketone solution), 〇 3 kg of HP403 2D ( Japan's INK Chemical Industry Co., Ltd., trade name), kg.5kg of NC3000 (manufactured by Nippon Kayaku Co., Ltd., trade name) (tree 曰 形 · 50 50% by mass of methyl ethyl hydrazine solution), and 0.8 g 丨 cyanoethyl 2-ethyl-1-methylimidazole, and then added to 930lkg OP930 (manufactured by Clariant Co., Ltd., trade name), and kg15kg HP360 (made by Showa Denko Co., Ltd., trade name) After stirring for about 3 hours until the resin composition was uniform, it was allowed to stand at room temperature (25 ° C) for 24 hours to defoam to obtain a resin composition varnish. (Varnish mixture example 6) 25 ml with a cock attached to the reflux cooler a 1 liter separation flask with a moisture metering device, a thermometer, and a stirrer, and adding 3 4 8.5 g (0.85 mol) of BAPP as a diamine having 2 or more aromatic rings (2, 2 - double [4 one ( 4 -Aminophenoxy)phenyl]propane), 330_0g (0.15 mol) of X-22-1660B-3 as a nonoxyldiamine (trade name 'mine equivalent 2200 by Shin-Etsu Chemical Co., Ltd.) , 3 93.6§ (2.05mol) of TMA (trimellitic anhydride), and 2600g as non-quality Polar solvent of N M P (N - methyl-2 - pyrrolidone) 'to 8 0 -24- 200908820 t: for 30 minutes. Next, 500 ml of toluene which is an aromatic hydrocarbon azeotropeable with water was added, and the temperature was raised to reflux at about 16 ° C for 2 hours. Distilling water of 3 6.0 m 1 or more from the moisture quantitative receiver. After confirming that no new water was distilled off, the temperature was raised to about 19 (TC, toluene was removed. Thereafter, the obtained solution was recovered at room temperature, and 27 5.0 g was added. (1. lOmol) of MDI (4,4'-diphenylmethane diisocyanate) as an aromatic diisocyanate. After the solution, 19 (TC reaction for 2 hours. After the reaction is completed, polyiminamide is obtained. NMP solution of amine resin. NMP solution (resin solid content: 31.2% by mass) of 2.24 kg of polyamidoximine resin, and 0. 2 kg of EPPN5 0 2H (manufactured by Nippon Kayaku Co., Ltd.) Name) (resin solids are 50% by mass of methyl ethyl ketone solution), 3.3kg of HP40 3 2D (made by Dainippon INK Chemical Industry Co., Ltd., trade name), 〇5kg of NC3000 (Nippon Chemicals) Co., Ltd., the product name) (resin solids are 50% by mass of methyl ethyl ketone solution), and 8.8g of 1-cyanoethyl-2-ethyl- 1 -methylimidine, and then Add 0.1kg of OP930 (made by Clariant, trade name), and 515kg of HP3 60 ( And the company made by Electrician Co., Ltd., trade name), stir for about 3 hours until the resin composition is uniform. Then, it is allowed to stand at room temperature (25 °C) for 24 hours to defoam to obtain a resin composition varnish. ) Made of glass cloth WEX - 1〇27 (made by Asahi Shuebel Co., Ltd., trade name 'thickness: 9 vm) on both sides of the main surface, coated with a vertical coater - 25 - 200908820 cloth varnish with the first example The varnish of the resin composition is made to have a total content of 55//m' after drying, and is heated and dried by a drying oven of 1 Torr to 14 Torr for a retention time of 7 1% by mass. Preform (P 1 ). A varnish was used in the same manner as in each of the resin varnishes prepared in Examples 2 to 6 to obtain a prepreg having a resin content of 71% by mass (P 2 〜 (Production of Resin Film) to Poly(p-phenylene) Ethylene glycol dicarboxylate (pET) film (Teiren Co., Ltd.'s trade name: Purex31) above. The varnish was blended with the resin composition varnish of Example 1 and applied to a dry mold by a die-casting coater. // m '1' 〇 0~1 4 〇〇c drying oven to make it stay for 5 minutes The resin film F1 was obtained by heating and drying, and the resin varnishes of the resin compositions prepared in Examples 2 to 6 were used to obtain resin thin films (F2 to F6). (Example 1) The thickness was 1 2 // One of the m pairs of electrolytic copper foil (manufactured by Sakamoto Electrolysis Co., Ltd., trade name: HL A - 12) is wrapped with prepreg P1, respectively on the main faces (vertical faces perpendicular to the thickness direction) of the pre-material P1 The laminated electrolytic copper foil 'has a heating rate of 5. (: / /, forming temperature is 2 3 0 t, shape pressure is 4 MPa, molding time is 7 〇 minutes, vacuum degree is 40 hPa condition 'pressurize' to make two-sided copper-clad laminate. One side of the plywood (thickness in the thickness direction 10 immersion group P6 has a thick film clearing film immersed in the sag -26-200908820 straight face), by uranium engraving, the line width is 5 0 " m In this case, a conductive pattern circuit is formed on a surface parallel to the main surface so that the angle between the direction in which the glass fibers are disposed (longitudinal direction) and the longitudinal direction of the conductive pattern circuit are respectively 4 5 degrees. On the surface opposite to the surface on which the conductive pattern circuit is formed, a full uranium engraving treatment is performed to remove the copper foil, and a substrate material having a conductive pattern circuit on one main surface is formed. On the surface of the pattern, the resin film F1 and the electrolytic copper foil (manufactured by Nippon Electrolysis Co., Ltd., trade name: HLA-12) were laminated in this order, and the temperature increase rate was 5 ° C /min, and the molding temperature was 23 0. , forming pressure is 4MPa, into The time was 70 minutes, and the vacuum was 40 hPa, and the pressure was applied. The surface copper foil of the laminate obtained by pressurization was removed to obtain an evaluation substrate coated with a conductive pattern circuit (Examples 2 to 6). An evaluation substrate was obtained in the same manner as in Example 1 except that the prepreg P1 to P6 were used instead of the prepreg P1 and the resin films F2 to E6, respectively, in the same manner as in Example 1. (Example 7) The thickness was 12/zm. A pair of electrolytic copper foil (trade name: HLA - 12 manufactured by Nippon Electrolysis Co., Ltd.) is used to sandwich the prepreg P1, and the electrolytic copper foil is laminated on the main surfaces of both sides of the prepreg P1 at a temperature increase rate. At 25 ° C / min, a forming temperature of 230 ° C, a forming pressure of 4 MPa, a molding time of 70 minutes, and a vacuum of 40 hPa, pressurization was carried out to produce two -27-200908820 copper-clad laminates. A conductive pattern circuit having a line width of 50 / zm is formed by etching on one side main surface of the double-sided copper-clad laminate. At this time, a conductive pattern circuit is formed on a surface parallel to the main surface to make a The direction of the side of the glass fiber (the first direction) and The angle formed by the longitudinal direction (conduction direction) of the conductive pattern circuit is 30 degrees (the angle between the direction of the glass fiber disposed on the other side and the longitudinal direction of the conductive pattern circuit is 60 degrees). The surface opposite to the surface of the circuit was subjected to a comprehensive etching treatment to remove the copper foil 'a substrate material having a conductive pattern circuit formed on one main surface. The evaluation substrate was produced in the same manner as in Example 1 using the substrate material. 8 to 10) An evaluation substrate was obtained in the same manner as in Example 7 except that the prepreg P 2 to P 4 were used instead of the prepreg P 1 and the resin films F2 to 4 in place of the resin film f 1 . (Comparative Examples 1 to 4) A P-type 7 & one side of the two-sided foil-clad laminate was formed on the side surface parallel to the main surface to form a conductive pattern circuit to arrange the glass fibers on one side (Fig. 3 a The evaluation substrate was produced in the same manner as in Examples 1 to 4 except that the angle formed by the longitudinal direction (conduction direction) of the conduction pattern circuit (the θ1 in FIG. 3) was 90 degrees. (Evaluation of Flexibility) -28- 200908820 Evaluation substrates of Examples 1 to 10 and Comparative Examples 1 to 4 were evaluated using an MIT tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: 2 1 2 1 0 1 1 - 00) Flexibility. In this evaluation test, the direction of the bend (Fig. 1, 3, B direction) is at an angle (0!) to the arrangement direction of one side of the glass fiber (fiber 6 of Fig. 1, fiber 76 of Fig. 3) (Fig. 1 or Fig. 3) 01) and the angle of the bend (02) with the arrangement direction of the other side glass fiber (fiber 8 of Fig. 1, fiber 7 8 of Fig. 3) (θ2 of Fig. 1, not shown in Fig. 3) It is shown in Table 1 and Table 2. Further, the bending direction is the same as the longitudinal direction of the conductive pattern circuit. The number of times of bending to the disconnection of the conductive pattern circuit and the number of times the substrate was broken were measured with respect to the bending radius of 0.38 mm or 1.00 mm, with a weight of 500 g, a bending angle of 135 degrees, and a speed of 1 75 cpm. In addition, the presence or absence of a fracture system was determined visually. The results are shown in Tables 1 and 2. (Evaluation of resistance to torsion) The evaluation substrates of Examples 1 to 10 and Comparative Examples 1 to 4 were evaluated for resistance to torsion. In this evaluation test, the end portion of the non-buckling portion on one side of the substrate is fixedly evaluated so that the long-side direction of the conductive pattern circuit is parallel to the axial direction of the twist, and the end portion of the other non-buckling portion is applied with 50. The weighting state of 0 g was evaluated to the number of times the fiber substrate was broken at a twist angle of +135 degrees to 135 degrees. In addition, the presence or absence of a fracture system was determined visually. The results are shown in Table 1 '2. -29- 200908820 [IS Embodiment 10 Z § »·〇Ό >30000 602 >50000 >20000 Embodiment 9 CU § 沄>30000 487 >50000 >20000 Embodiment 8 (N Cu. S Os >30000 473 >50000 >20000 Embodiment 7 S: 1 >30000 i ί-Η >50000 >20000 Embodiment 6 Ό Oh 00 ] >30000 ί 689 >50000 1 i >20000 Implementation Example 5 ίη Οι CN 〇〇>30000 640 >50000 >20000 Embodiment 4 2 00 1 >30000 , 652 >50000 >20000 Embodiment 3 ΓΛ Ο. CN >30000 570 >50000 > 20000 Example 2 (Ν >30000 545 >50000 >20000 Example 1 € 〇〇>30000 OO in >50000 i >20000 Prepreg angle Θ! (degrees) Angle θ2 (degrees) MIT test 1 (times) (Note 1) MIT test 2 (times) (Note 2) MIT test 3 (times) (Note 3) MIT test 4 (times) (Note 4) Resistance to torsion (times).皲蝱堪«a^>&-lmasl9I:IH^siruttl).镰^租岛^Camel maple awake»Domain_. Day 00.1: 靼和租||(£玥). Manganese shirt for rent忉 忉 蝱 匣 匣 匣 。 。 。 。 。 。 。 。 Nd: ® and rent ifu+H).镰衫租铝忉#0矿蝱机械@1»敏^. " 日:_和«&(1坩) -30- 200908820 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Prepreg Ρ 1 Ρ 2 Ρ 3 Ρ 4 Angle 1 (degrees) 90 90 90 90 Angle θ2 (degrees) 0 0 0 0 ΜΙΤ test 1 (times) (Note 1) 19 16 25 40 ΜΙΤ test 2 (times) (Note 2) 8323 8100 10254 10527 ΜΙΤ test 3 (times) (Note 3) 197 188 185 230 ΜΙΤ test 4 (times) (Note 4) 15132 13501 18644 17546 Resistance to torsion (times) 8812 8725 13217 13362 (Note 1) Bending radius: 〇.38 mm. The number of times of bending when the conductive pattern is broken. (Note 2) Bending radius: 0.38 mm. The number of times of bending to the evaluation substrate. (Note 3) Bending radius: 1.00 mm. The number of times of bending when the conductive pattern is broken. (Note 4) Bending radius: 1.00 mm According to the present invention, it is possible to provide a printed wiring board which can be flexibly arbitrarily and which has sufficient dimensional stability and sufficiently improves folding resistance, and has a flexing Electronic device for printed wiring board of the above characteristics. [Simplified description of the drawing] [Fig. 1] shows the present invention A view of a suitable embodiment of a printed wiring board. [Fig. 2] A side view of a meandering printed wiring board. [Fig. 3] A top view of a conventional warped printed wiring board. [Key element symbol description] -31 - 200908820 2 : Fibrous base material layer 4 : Conductor 6 : First fiber 8 : Second fiber 20 : Non-bending portion 40 = Bending portion 100, 300 : Printed wiring board - 32

Claims (1)

200908820 十、申請專利範圍 1 · 一種印刷配線板，其於預定折曲方向折曲的 線板’其特徵爲具備含有配置於第1方向的第1纖 維基材、與形成於該纖維基材上的導體層，該第i 配置成使該第1方向與該折曲方向所成角度爲30 〇 2 .如申請專利範圍第1項之印刷配線板，其中 基材更含有配置於與該第1方向交叉的第2方向之 維。 3 .如申請專利範圍第2項之印刷配線板，其中 纖維爲配置成使該第2方向與該折曲方向所成角芳 〜6 0度。 4.如申請專利範圍第1項至第3項中任一項之 線板，其中該纖維爲玻璃布，該纖維基材的厚度爲 以下。 5 .如申請專利範圍第1項至第4項中任一項之 線板，其中該纖維基材中含浸有熱硬化性樹脂。 6.如申請專利範圍第5項之印刷配線板，其中 化性樹脂含有具有縮水甘油基的樹脂。 7 .如申請專利範圍第5項或第6項之印刷配線 中該熱硬化性樹脂含有具有醯胺基的樹脂。 8 ·如申請專利範圍第5項至第7項中任一項之 線板，其中該熱硬化性樹脂含有具有矽氧烷鍵的聚 亞胺樹脂。 印刷配 維之纖 纖維爲 、6 0度 該纖維 第2纖 該第2 【爲30 印刷配 5 0 /z m 印刷配 該熱硬 板，其 印刷配 醯胺醯 -33- 200908820 9.如申請專利範圍第5項之印刷配線板，其中該熱硬 化性樹脂含有丙烯酸樹脂。 1 〇 . —種電子機器，其特徵爲具備於預定的該折曲方 向經折曲之如申請專利範圍第1項至第9項中任一項之印 刷配線板。 -34-200908820 X. Patent Application No. 1 A printed wiring board having a first fiber substrate disposed in a first direction and formed on the fiber substrate, wherein the wire plate is bent in a predetermined bending direction The conductor layer is disposed such that the first direction is at an angle of 30 〇2 to the bending direction. The printed wiring board according to claim 1, wherein the substrate further comprises the first substrate. The dimension of the second direction in which the directions intersect. 3. The printed wiring board of claim 2, wherein the fibers are disposed such that the second direction forms an angle of ～60 degrees with the bending direction. 4. A wire plate according to any one of claims 1 to 3, wherein the fiber is a glass cloth, and the fiber substrate has a thickness of the following. A wire plate according to any one of claims 1 to 4, wherein the fiber base material is impregnated with a thermosetting resin. 6. The printed wiring board of claim 5, wherein the chemical resin contains a resin having a glycidyl group. 7. The printed circuit of claim 5 or 6, wherein the thermosetting resin contains a resin having a guanamine group. The wire plate according to any one of the items 5 to 7, wherein the thermosetting resin contains a polyimide resin having a siloxane chain. The fiber of the printing and matching fabric is 60 degrees, the second fiber of the fiber is the second one. [The 30-printing is equipped with 50/zm printing and the hot hard plate is printed, and the printing is equipped with amidoxime-33-200908820. The printed wiring board of item 5, wherein the thermosetting resin contains an acrylic resin. An electronic device characterized by being provided with a printed wiring board according to any one of claims 1 to 9 in a predetermined bending direction. -34-